Hair colorant compositions comprising 2-methoxymethyl-1,4-diaminobenzene and 2,6-diaminopyridine, methods, and kits comprising the compositions

ABSTRACT

A hair colorant composition comprises 2,6-diaminopyridine coupler in combination with 2-methoxymethyl-1,4-diaminobenzene developer. A kit for coloring hair comprises the hair colorant composition. A method of treating hair comprises applying the hair colorant composition to hair.

TECHNICAL FIELD

The present invention relates generally to hair colorant compositionsand, more specifically, to oxidative hair colorant compositionscontaining a combination of a 2-methoxymethyl-1,4-diaminobenzenedeveloper with 2,6-diaminopyridine, methods for treating hair with theoxidative hair colorant compositions, and hair coloring kits comprisingthe oxidative hair colorant compositions.

BACKGROUND

The permanent alteration of the color of keratinous fibers, inparticular human hair, by the application of hair dyes is well known.Oxidative hair dye precursors, i.e., developers (also called primaryintermediates) and couplers diffuse into the hair through the cuticleand into the cortex. The precursors combine in the presence of anoxidizing agent, such as hydrogen peroxide, to form larger-sized dyemolecules that result in a visual color of the hair (“end hair color”).Different combinations of developers and couplers produce differentshades of hair color when combined with the oxidizing agent. The endhair color is not easily predicted given the complex chemical processthat occurs to achieve an end hair color.

Permanent hair colorant formulations should produce end hair colors thatare stable for at least 4 to 6 weeks. Additionally, the end hair colorshould exhibit good washfastness, good lightfastness, fastness torubbing, as well as sufficient resistance with respect to perspiration.Preferably, it should be possible to produce a broad palette ofdifferent color shades by combining suitable developers and couplers.

Hair colorant formulations generally provide acceptable and immediateresults. However, achieving both desired shade (hue) and depth of shade(chroma) remains challenging, particularly for hair colorantformulations that impart a blue with less violet overtones to the hair.To achieve desirable shades in the blue area, a combination of1-4-diaminobenzene compounds with 2,6-diaminopyridine may be used.Nevertheless, the shades may fail to provide the desirable hue andchroma and, thereby, the hair colorant formulation may fall short ofproducing the desired end hair color.

U.S. Pat. No. 3,200,040 discusses the dyeing of hair with coupler andprimary compounds based on diaminopyridines. The combination ofp-toluenediamine with 2,6-diaminopyridine in an aqueous ammonia solutionand mixed with 6% hydrogen peroxide gives a strong blue color. There areother developers used that give different shades of blue, but they maynot be available to use from a toxicological standpoint and may givevery different performance with other couplers compared to1,4-diaminobenzene based developers, which increases the complexity ofdevelopment for marketable hair color formulations.

There remains an ongoing need for additional hair colorant compositionsthat can provide desirable blue shades with less violet overtones,particularly when used with various oxidant systems, i.e., ammoniumcarbonate, hydrogen peroxide, and, optionally, a radical scavengerand/or chelant.

SUMMARY

Embodiments described herein relate to a hair colorant compositioncomprising: (a) 2,6-diaminopyridine coupler and/or its cosmeticallyacceptable salts and (b) 2-methoxymethyl-1,4-diaminobenzene developerand/or its cosmetically acceptable salts and (c) an oxidizing agent.

Further embodiments described herein relate to a method of treatinghair. The method comprises contacting hair with a hair colorantcomposition resulting from mixing a first composition and a secondcomposition comprising an oxidizing agent. The first compositioncomprises a 2,6-diaminopyridine coupler and/or its cosmeticallyacceptable salts and 2-methoxymethyl-1,4-diaminobenzene developer and/orits cosmetically acceptable salts.

Still further embodiments described herein relate to a hair coloring kitcomprising an individually packaged oxidizing component and anindividually packaged dye component. The individually packaged oxidizingcomponent comprises an oxidizing agent. The individually packaged dyecomponent comprises 2,6-diaminopyridine and/or its cosmeticallyacceptable salts and 2-methoxymethyl-1,4-diaminobenzene developer and/orits cosmetically acceptable salts.

These and other features, aspects, and advantages of the presentinvention will become better understood with reference to the followingdetailed description and appended claims.

DETAILED DESCRIPTION

As used herein, the term “hair” in the context of the oxidative haircolorant compositions and their uses according to various embodiments,encompasses without limitation keratin-containing fibers that may beregarded as “living,” i.e., on a living body, or as “non-living,” i.e.,in a wig, hairpiece, or other aggregation of non-living keratinousfibers. Though mammalian hair is preferred, human hair being aparticular example thereof, it will be understood that also wool, fur,and other keratin-containing fibers are suitable substrates for thecompositions described herein.

As used herein, the term “cosmetically acceptable salts” means saltswhich are suitable for use in contact with the skin or hair of humansand lower animals without undue toxicity, incompatibility, instability,irritation, allergic response, and the like for example chlorides,bromides, sulfates, malates, tartrates, lactates, acetates andhemisulfates.

As used herein, unless clearly indicated otherwise by context, termsreferring to particular coupler, developer, and oxidizing compounds arebroad enough to encompass not only the particular chemical compounditself, but also its cosmetically acceptable salts and/or mixturesthereof. For example, the term “2,6-diaminopyridine” should beinterpreted to include not only 2,6-diaminopyridine, but also itscosmetically acceptable salts and/or mixtures thereof.

Hair Colorant Composition

A hair colorant composition comprises (a) 2,6-diaminopyridine couplerand (b) 2-methoxymethyl-1,4-diaminobenzene developer and (c) anoxidizing agent. The 2,6-diaminopyridine coupler has the formula (I):

Based on the weight of the oxidative hair colorant composition, the haircolorant composition may comprise up to 12% by weight, or from 0.001% to12%, or from 0.001% to 6%, or from 0.05% to 6% by weight, of2,6-diaminopyridine.

The developer 2-methoxymethyl-1,4-diaminobenzene is represented byformula (II) as follows:

Based on the weight of the hair colorant composition, the hair colorantcomposition may comprise up to 12% by weight, or from 0.001% to 12%, orfrom 0.001% to 6%, or from 0.05% to 6% by weight, of the developer. Inone embodiment, the hair colorant composition may comprise a total of upto 12% by weight, or from 0.001% to 12%, or from 0.001% to 6%, or from0.05% to 6% by weight, of 2,6-diaminopyridine and the developercombined.

It has been found that the specific combination of 2,6-diaminopyridineand 2-methoxymethyl-1,4-diaminobenzene, when incorporated into a haircolorant composition, imparts desirable blue shades with less violetovertones than comparable compositions with other 1,4-benzenediamineanalogues.

Oxidizing Agent

The hair colorant composition may comprise at least one source of anoxidizing agent. Preferred oxidizing agents for use herein are watersoluble peroxygen oxidizing agents. Water-soluble peroxygen oxidizingagents are well known in the art and include hydrogen peroxide,inorganic alkali metal peroxides such as sodium periodate and sodiumperoxide and organic peroxides such as urea peroxide, melamine peroxide,and inorganic perhydrate salt bleaching compounds, such as the alkalimetal salts of perborates, percarbonates, perphosphates, persilicates,persulfates and the like. These inorganic perhydrate salts may beincorporated as monohydrates, tetrahydrates etc. Alkyl and arylperoxides, and or peroxidases, oxidase, and uricases and theirsubstrates may also be used. Mixtures of two or more such oxidizingagents can also be used if desired. The oxidizing agents may be providedin aqueous solution or as a powder which is dissolved prior to use.Preferred for use in the hair colorant compositions are hydrogenperoxide, percarbonate, persulfates and combinations thereof.

In one embodiment, the hair colorant composition comprises from 0.1% to20% by weight, or from 1% to 15% by weight, or from 2% to 10% by weightof oxidizing agent.

A potential oxidizing agent for use herein is a source ofperoxymonocarbonate ions formed in situ from a source of hydrogenperoxide and a hydrogen carbonate ion source. Moreover, this system isalso particularly effective in combination with a source of ammonia orammonium ions. Accordingly, any source of these peroxymonocarbonate ionsmay be used. Suitable sources for use herein include sodium, potassium,guanidine, arginine, lithium, calcium, magnesium, barium, ammonium saltsof carbonate, carbamate and hydrocarbonate ions and mixtures thereofsuch as sodium carbonate, sodium hydrogen carbonate, potassiumcarbonate, potassium hydrogen carbonate, guanidine carbonate, guanidinehydrogen carbonate, lithium carbonate, calcium carbonate, magnesiumcarbonate, barium carbonate, ammonium carbonate, ammonium hydrogencarbonate and mixtures thereof. Percarbonate salts may be used both asan oxidizing agent and as a source of carbonate ions. Preferred sourcesof carbonate ions, carbamate and hydrocarbonate ions are sodium hydrogencarbonate, potassium hydrogen carbonate, ammonium carbamate, andmixtures thereof.

The oxidative agent may comprise from 0.1% to 15% by weight, or from 1%to 10% by weight, or from 1% to 8% by weight of a hydrogen carbonateion; and from 0.1% to 10% by weight, or from 1% to 7% by weight, or from2% to 5% by weight of the oxidative agent of a source of hydrogenperoxide.

Optional Additional Dye Components

The hair colorant composition may contain additional dye components thatmay be selected from those known in the art, for example, one or moredirect dyes, one or more oxidative dye precursors, or mixtures thereof.

Optional Direct Dyes

The hair colorant compositions may further comprise compatible directdyes, in an amount sufficient to provide or enhance coloring,particularly with regard to intensity. Typically, such an amount willrange from 0.05% to 4%, by weight of the hair colorant composition.

Suitable direct dyes include but are not limited to: Acid dyes such asAcid Yellow 1, Acid Orange 3, Acid Black 1, Acid Black 52, Acid Orange7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Violet 43, HC Blue 16,Acid Blue 62, Acid Blue 25, Acid Red 4, Basic Dyes such as Basic Brown17, Basic Red 118, Basic Orange 69, Basic Red 76, Basic Brown 16, BasicYellow 57, Basic Violet 14, Basic Blue 7, Basic Blue 26, Basic Red 2,Basic Blue 99, Basic Yellow 29, Basic Red 51, Basic Orange 31, BasicYellow 87,4-(3-(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl)-4-methylmorpholin-4-ium-methylsulfate,(E)-1-(2-(4-(4,5-dimethylthiazol-2-yl)diazenyl)phenyl)(ethyl)amino)ethyl)-3-methyl-1H-imidazol-3-iumchloride,(E)-4-(2-(4-(dimethylamino)phenyl)diazenyl)-1-methyl-1H-imidazol-3-ium-3-yl)butane-1-sulfonate,(E)-4-(4-(2-methyl-2-phenylhydrazono)methyl)pyridinium-1-yl)butane-1-sulfonate,N,N-dimethyl-3-(4-(methylamino)-9,10-dioxo-4a,9,9a,10-tetrahydroanthracen-1-ylamino)-N-propylpropan-1-aminiumbromide, Disperse Dyes such as Disperse Red 17, Disperse Violet 1,Disperse Red 15, Disperse Violet 1, Disperse Black 9, Disperse Blue 3,Disperse Blue 23, Disperse Blue 377, Nitro Dyes such as1-(2-(4-nitrophenylamino)ethyl)urea,2-(4-methyl-2-nitrophenylamino)ethanol, 4-nitrobenzene-1,2-diamine,2-nitrobenzene-1,4-diamine, Picramic acid, HC Red No. 13,2,2′-(2-nitro-1,4-phenylene)bis(azanediyl)diethanol, HC Yellow No. 5, HCRed No. 7, HC Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HC OrangeNo. 1, HC Red No. 1,2-(4-amino-2-chloro-5-nitrophenylamino)ethanol, HCRed No. 3,4-amino-3-nitrophenol, 4-(2-hydroxyethylamino)-3-nitrophenol,2-amino-3-nitrophenol, 2-(3-(methylamino)-4-nitrophenoxy)ethanol,3-(3-amino-4-nitrophenyl)propane-1,2-diol, HC Yellow No. 11, HC VioletNo. 1, HC Orange No. 2, HC Orange No. 3, HC Yellow No. 9, HC Red No. 10,HC Red No. 11, 2-(2-hydroxyethylamino)-4,6-dinitrophenol, HC Blue No.12, HC Yellow No. 6, HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7,HC Yellow No. 10, HC Blue No. 9,2-chloro-6-(ethylamino)-4-nitrophenol,6-nitropyridine-2,5-diamine, HC Violet No.2,2-amino-6-chloro-4-nitrophenol,4-(3-hydroxypropylamino)-3-nitrophenol, HC Yellow No. 13,6-nitro-1,2,3,4-tetrahydroquinoxaline, HC Red No. 14, HC Yellow No. 15,HC Yellow No. 14, N2-methyl-6-nitropyridine-2,5-diamine,N1-allyl-2-nitrobenzene-1,4-diamine, HC Red No. 8, HC Green No. 1, HCBlue No. 14, and Natural dyes such as Annato, Anthocyanin, Beetroot,Carotene, Capsanthin, Lycopene, Chlorophyll, Henna, Indigo, Cochineal.

The hair colorant compositions may include additional oxidative dyecompounds in the form of primary intermediates or couplers, hereinreferred to as oxidative dye precursors. Oxidative dye precursors may befree bases or the cosmetically acceptable salts thereof. It is to beunderstood that the additional precursors are detailed below only by wayof example and are not intended to limit the hair colorant compositionsor sub-components such as a tint compositions therein.

Suitable primary intermediates for use in the compositions describedherein include, but are not limited to: toluene-2,5-diamine,p-phenylenediamine, N-phenyl-p-phenylenediamine,N,N-bis(2-hydroxyethyl)-p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine),2-(1,2-dihydroxyethyl)-p-phenylenediamine,2,2′-(2-(4-aminophenylamino)ethylazanediyl)diethanol,2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol,2-(7-amino-2H-benzo[b][1,4]oxazin-4(3H)-yl)ethanol,2-chloro-p-phenylenediamine, p-aminophenol, p-(methylamino)phenol,4-amino-m-cresol, 6-amino-m-cresol, 5-ethyl-o-aminophenol,2-methoxy-p-phenylenediamine, 2,2′-methylenebis-4-aminophenol,2,4,5,6-tetraminopyrimidine, 2,5,6-triamino-4-pyrimidinol,1-hydroxyethyl-4,5-diaminopyrazole sulfate,4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole,4,5-diamino-1-isopropylpyrazole, 4,5-diamino-1-butylpyrazole,4,5-diamino-1-pentylpyrazole, 4,5-diamino-1-benzylpyrazole,2,3-diamino-6,7-dihydropyrazolo[1,2-a]pyrazol-1(5H)-onedimethosulfonate, 4,5-diamino-1-hexylpyrazole,4,5-diamino-1-heptylpyrazole and mixtures thereof.

Suitable couplers for use in the compositions described herein include,but are not limited to: resorcinol, 4-chlororesorcinol,2-chlororesorcinol, 2-methylresorcinol, 4,6-dichlorobenzene-1,3-diol,2,4-dimethylbenzene-1,3-diol, m-aminophenol, 4-amino-2-hydroxytoluene,2-methyl-5-hydroxyethylaminophenol, 3-amino-2,6-dimethylphenol,3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-cresol,6-hydroxybenzomorpholine, 2-amino-5-ethylphenol, 2-amino-5-phenylphenol,2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol,5-methyl-2-(methylamino)phenol, 2,4-diaminophenoxyethanol,2-amino-4-hydroxyethylaminoanisole,1,3-bis-(2,4-diaminophenoxy)-propane,2,2′-(2-methyl-1,3-phenylene)bis(azanediyl)diethanol,benzene-1,3-diamine, 2,2′-(4,6-diamino-1,3-phenylene)bis(oxy)diethanol,3-(pyrrolidin-1-yl)aniline, 1-(3-(dimethylamino)phenyl)urea,1-(3-aminophenyl)urea, 1-naphthol, 2-methyl-1-naphthol,1,5-naphthalenediol, 2,7-naphthalenediol or1-acetoxy-2-methylnaphthalene, 4-chloro-2-methylnaphthalen-1-ol,4-methoxy-2-methylnaphthalen-1-ol, 2,6-dihydroxy-3,4-dimethylpyridine,2,6-dimethoxy-3,5-pyridinediamine,3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine,2,6-diaminopyridine, pyridine-2,6-diol, 5,6-dihydroxyindole,6-hydroxyindole, 5,6-dihydroxyindoline,3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, 1,2,4-trihydroxybenzene,2-(benzo[d][1,3]dioxol-5-ylamino)ethanol (also known ashydroxyethyl-3,4-methylenedioxyaniline), and mixtures thereof.

The total quantity of the additional oxidative dye precursors containedin the hair colorant composition, or sub-component thereof, may be up to12% by weight, especially from 0.05% to 6% by weight of the haircolorant composition.

Solvent

The hair colorant composition may comprise solvents such as water, loweraliphatic alcohols, for example aliphatic alcohols with from 1 to 4carbon atoms such as ethanol, propanol and isopropanol, aromaticalcohols such as benzyl alcohol and phenoxyethanol or polyols or polyethers such as glycerin and 1,2- and 1,3-propyleneglycol, carbitol,2-butoxyethanol, diethylene glycol, monoethyl ether, monomethyl ether,hexylene glycol, ethylene glycol, ethoxy glycol, butoxydiglycol,ethoxydiglycerol, dipropyleneglycol and polyglycerol. The solvents maybe utilized for the hair colorant composition or in sub-components suchas in a tint composition or an oxidizing composition in concentrationsof from 0.1% to 30% by weight.

pH-Modifying Agents

The hair colorant composition, generally in a tint composition packagedseparately from the oxidizing agent (e.g., oxidizing composition), maycomprise a pH-modifying agent such as an alkalizing agent.

Any alkalizing agent known in the art may be used such as:alkanolamines, for example monoethanolamine, diethanolamine,triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3-propanediol; guanidium salts; andalkali-metal and ammonium hydroxides and carbonates, such as sodiumhydroxide and ammonium carbonate. Particularly, preferred alkalizingagents are those which provide a source of ammonium ions.

Any source of ammonium ions is suitable for use herein. Preferredsources of ammonium ions include ammonium chloride, ammonium sulfate,ammonium nitrate, ammonium phosphate, ammonium acetate, ammoniumcarbonate, ammonium hydrogen carbonate, ammonium carbamate, ammoniumhydroxide, percarbonate salts, ammonia and mixtures thereof.Particularly preferred are ammonium carbonate, ammonium carbamate,ammonia, and mixtures thereof.

The hair colorant composition or the tint composition may comprise from0.1% to 10% by weight, such as from 0.5% to 5%, such as from 1% to 3% ofan alkalizing agent, such as a source of ammonium ions.

pH

The hair colorant compositions described above may have a pH of from 7to 12, preferably from 8 to 11. For embodiments comprising aperoxymoncarbonate ion, the pH is preferably up to and including pH 9.5,more preferably from 7.5 to 9.5, even more preferably from 8.4 to 9.5,most preferably from 8.5 to 9.4, for example, 9.0 or 9.3.

Any sub-components of the hair colorant compositions, such as a tintcomposition or an oxidizing composition, may have a different pH fromthe hair colorant composition. For example, if the tint compositioncomprises an alkalizing agent, the tint composition will have analkaline pH, such as higher than 7. The oxidizing composition maycomprise an acidic pH of less than 7.

The pH of the hair colorant compositions can be determined by usingeither a Mettler Toledo MP220 or a MP225 pH equipment, fitted with astandard laboratory pH electrode. The equipment is calibrated beforeeach use using standard calibration buffers and using the standardcalibration procedure.

Optional Chelants

Suitable optional chelants for use in hair colorant compositions arecarboxylic acids (in particular aminocarboxylic acids) and phosphonicacids (in particular aminophosphonic acids) and polyphosphoric acids(e.g., linear polyphosphoric acids), including the salts and derivativesof these chelants. Generally, the chelants do not penetrate the hair toany significant extent under typical oxidative hair coloring conditions.As such, the chelants generally do not affect color formation inside thehair.

The hair colorant compositions may comprise from 0.01% to 5%, in someembodiments, from 0.25% to 3%, in certain embodiments, from 0.5% to 1%of chelant, salts thereof, derivatives thereof, or mixtures thereof.

The hair colorant compositions may comprise an aminocarboxylic acidchelant. Aminocarboxylic acid chelants as defined herein are chelantshaving at least one carboxylic acid moiety (—COOH) and at least onenitrogen atom. Examples of aminocarboxylic acid chelants suitable foruse herein include diethylenetriamine pentaacetic acid (DTPA),ethylenediamine disuccinic acid (EDDS), ethylenediamine diglutaric acid(EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS),glycinamide-N,N′-disuccinic acid (GADS), ethylenediamine-N—N′-diglutaricacid (EDDG), 2-hydroxypropylenediamine-N—N′-disuccinic acid (HPDDS),ethylenediaminetetraacetic acid (EDTA), ethylenedicysteic acid (EDC),ethylenediamine-N—N′-bis(o-hydroxyphenyl acetic acid) (EDDHA),diaminoalkyldi(sulfosuccinic acids) (DDS),N,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid (HBED),salts thereof and derivatives thereof.

Other suitable aminocarboxylic type chelants for use herein areiminodiacetic acid derivatives such as N-2-hydroxyethyl-N,N diaceticacid or glyceryl imino diacetic acid, iminodiaceticacid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethylN-2-hydroxypropyl-3-sulfonic acid, β-alanine-N,N′-diacetic acid,aspartic acid-N,N′-diacetic acid, aspartic acid-N-monoacetic acid andiminodisuccinic acid chelants, ethanoldiglycine acid, salts thereof andderivatives thereof. Dipicolinic acid and2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable.

In further embodiments, the hair colorant compositions may comprise from0.1% to 5% of diethylenetriaminepenta(methylenephosphonic acid) and from0.1% to 5% of ethylenediamine-N,N′-disuccinic acid, and from 0.1% to 5%of diethylenetriaminepentaacetic acid. Preferred for use herein isethylenediamine-N,N′-disuccinic acid (EDDS), derivatives and saltsthereof.

The hair colorant compositions may comprise a chelant selected fromaminophosphonic acid type chelants, salts thereof, derivatives thereofand mixtures thereof. Amino-phosphonic acid type chelants are defined aschelants comprising an aminophosphonic acid moiety (—PO₃H₂) or itsderivative —PO₃R² wherein R² is a C₁ to C₆ alkyl or aryl radical.

Suitable aminophosphonic acid type chelants for use herein areaminotri-(1-ethylphosphonic acid),ethylenediaminetetra-(1-ethylphosphonic acid),aminotri-(1-propylphosphonic acid), and aminotri-(isopropylphosphonicacid). Preferred chelants for use herein areaminotri-(methylenephosphonic acid),ethylenediaminetetra(methylenephosphonic acid) (EDTMP) anddiethylene-triamine-penta-(methylenephosphonic acid) (DTPMP) andmixtures thereof.

Optional Radical Scavenger

The hair colorant compositions may further comprise a source of radicalscavenger. As used herein, the term “radical scavenger” refers to aspecies that can react with a radical, e.g. a carbonate radical, toconvert the radical by a series of fast reactions to a less reactive, orunreactive, species.

Suitable radical scavengers for use herein may be selected from theclasses of alkanolamines, amino sugars, amino acids, esters of aminoacids, pyrazolones, such as those discussed in US 2011/0035885A1 and US2011/0035886A1, and mixtures thereof. Particularly preferred compoundsare: monoethanolamine, 3-amino-1-propanol, 4-amino-1-butanol,5-amino-1-pentanol, 1-amino-2-propanol, 1-amino-2-butanol,1-amino-2-pentanol, 1-amino-3-pentanol, 1-amino-4-pentanol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropane-1,2-diol, glucosamine, N-acetylglucosamine, glycine,arginine, lysine, proline, glutamine, histidine, sarcosine, serine,glutamic acid, tryptophan, and mixtures thereof, and the salts such asthe potassium, sodium and ammonium salts thereof,3-carboxy-1H-pyrazol-5-one, 3-carboxy-1-phenyl-pyrazol-5-one,3-carboxy-1-(4-sulfophenyl)-pyrazol-5-one,3-carboxy-1-(4-carboxyphenyl)-pyrazol-5-one, and mixtures thereof.Preferred compounds are glycine, sarcosine, lysine, serine,2-methoxyethylamine, glucosamine, glutamic acid, morpholine, piperidine,ethylamine, 3-amino-1-propanol, and mixtures thereof. The hair colorantcompositions may comprise from 0.1% to 10% by weight, preferably from 1%to 7% by weight of the hair colorant composition of a radical scavenger.

Optional Conditioning Agent

The hair colorant composition may comprise a conditioning agent.Optionally, a separate conditioning composition comprising aconditioning agent may be used after the hair colorant composition.Conditioning agents suitable are selected from silicone materials,aminosilicones, fatty alcohols, polymeric resins, polyol carboxylic acidesters, cationic polymers, insoluble oils and oil derived materials andmixtures thereof. Additional materials include mineral oils and otheroils such as glycerin and sorbitol. Particularly useful conditioningmaterials are cationic polymers. Conditioners of cationic polymer typecan be chosen from those comprising units of at least one amine groupchosen from primary, secondary, tertiary and quaternary amine groupsthat may either form part of the main polymer chain, or be borne by aside substituent that is directly attached to the main polymer chain.Silicones can be selected from polyalkylsiloxane oils, linearpolydimethylsiloxane oils containing trimethylsilyl orhydroxydimethylsiloxane endgroups, polymethylphenylsiloxane,polydimethylphenylsiloxane or polydimethyldiphenylsiloxane oils,silicone resins, organofunctional siloxanes having in their generalstructure one or a number of organofunctional group(s), the same ordifferent, attached directly to the siloxane chain or mixtures thereof.Said organofunctional group(s) are selected from: polyethyleneoxy and/orpolypropyleneoxy groups, (per)fluorinated groups, thiol groups,substituted or unsubstituted amino groups, carboxylate groups,hydroxylated groups, alkoxylated groups, quaternium ammonium groups,amphoteric and betaine groups. The silicone can either be used as a neatfluid or in the form of a pre-formed emulsion.

The conditioning agent generally will be used at levels of from 0.05% to20% by weight of the hair coloring composition or the conditioningcomposition, such as from 0.1% to 15%, such as from 0.2% to 10%, such asfrom 0.2% to 2% by weight of the hair coloring composition or theconditioning composition.

Optional Polymer Thickener

According to the present invention, the hair coloring compositions maycomprise a polymer thickener, comprising at least one polymer selectedfrom associative polymers, polysaccharides, non-associativepolycarboxylic polymers, and mixtures thereof.

As used herein, the expression “associative polymers” means amphiphilicpolymers comprising both hydrophilic units and hydrophobic units, forexample, at least one C8 to C30 fatty chain and at least one hydrophilicunit. Associative polymers are capable of reversibly combining with eachother or with other molecules. Representative associative thickenersthat may be used are associative polymers chosen from:

(i) nonionic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit; (ii) anionic amphiphilicpolymers comprising at least one hydrophilic unit and at least onefatty-chain unit;

(iii) cationic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit; and

(iv) amphoteric amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit.

The nonionic amphiphilic polymers comprising at least one fatty chainand at least one hydrophilic unit may, for example, be chosen from:

celluloses modified with groups comprising at least one fatty chain; forexample: hydroxyethylcelluloses modified with groups comprising at leastone fatty chain chosen from alkyl, alkenyl and alkylaryl groups;

(2) hydroxypropyl guars modified with groups comprising at least onefatty chain;

(3) polyether urethanes comprising at least one fatty chain, such asC8-C30 alkyl or alkenyl groups;

(4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobicmonomers;

(5) copolymers of C1-C6 alkyl acrylates or methacrylates and ofamphiphilic monomers comprising at least one fatty chain;

(6) copolymers of hydrophilic acrylates or methacrylates and ofhydrophobic monomers comprising at least one fatty chain.

The anionic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit, may, for example, be chosen fromthose comprising at least one fatty-chain allyl ether unit and at leastone hydrophilic unit comprising an ethylenic unsaturated anionicmonomeric unit, for example, a vinylcarboxylic acid unit and further,for example, chosen from units derived from acrylic acids, methacrylicacids and mixtures thereof, wherein the fatty-chain allyl ether unitcorresponds to the monomer of formula (III) below:CH2=C(R1)CH2OBnR  (III)

in which R1 is chosen from H and CH3, B is an ethyleneoxy radical, n ischosen from zero and integers ranging from 1 to 100, R is chosen fromhydrocarbon-based radicals chosen from alkyl, alkenyl, arylalkyl, aryl,alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms,and, further, for example, from 10 to 24 carbon atoms and even further,for example, from 12 to 18 carbon atoms.

The anionic amphiphilic polymers may further be chosen, for example,from those comprising at least one hydrophilic unit of unsaturatedolefinic carboxylic acid type, and at least one hydrophobic unit of thetype such as a (C8-C30) alkyl ester or (C8-C30) oxyethylenated alkylester of an unsaturated carboxylic acid. The hydrophilic unit ofunsaturated olefinic carboxylic acid type corresponds to, for example,the monomer of formula (IV) below:CH2=C(R1)COOH  (IV)

in which R1 is chosen from H, CH3, C2H5 and CH2COOH, i.e. acrylic acid,methacrylic, ethacrylic and itaconic acid units. And the hydrophobicunit of the type such as a (C8-C30) alkyl ester or (C8-C30)oxyethylenated alkyl ester of an unsaturated carboxylic acid correspondsto, for example, the monomer of formula (V) below:CH2=C(R1)COOBnR2  (V)

in which R1 is chosen from H, CH3, C2H5 and CH2COOH (i.e. acrylate,methacrylate, ethacrylate and itaconate units), B is an ethyleneoxyradical, n is chosen from zero and integers ranging from 1 to 100, R2 ischosen from C8-C30 alkyl radicals, for example, C12-C22 alkyl radical.

Representative anionic amphiphilic polymers that can be used may furtherbe cross-linked The crosslinking agent can be a monomer comprising agroup of formula (VI) below:CH2=C<  (VI)

with at least one other polymerizable group whose unsaturated bonds arenot conjugated with respect to one another. Mention may be made, forexample, of polyallyl ethers such as polyallylsucrose and polyallylpentaerythritol.

The cationic amphiphilic polymers used are, for example, chosen fromquaternized cellulose derivatives and polyacrylates comprising aminoside groups. The quaternized cellulose derivatives are, for example,chosen from quaternized celluloses modified with groups comprising atleast one fatty chain, such as alkyl, arylalkyl and alkylaryl groupscomprising at least 8 carbon atoms, and mixtures thereof, quaternizedhydroxyethylcelluloses modified with groups comprising at least onefatty chain, such as alkyl, arylalkyl and alkylaryl groups comprising atleast 8 carbon atoms, and mixtures thereof. The alkyl radicals borne bythe above quaternized celluloses and hydroxyethylcelluloses, forexample, contain from 8 to 30 carbon atoms. The aryl radicals, forexample, are chosen from phenyl, benzyl, naphthyl and anthryl groups.

Among amphoteric amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit, mention may be made,for example, of methacrylamidopropyltrimethylammonium chloride/acrylicacid/C8-C30 alkyl methacrylate copolymers, wherein the alkyl radical is,for example, a stearyl radical.

Preferable associative polymeric thickeners for use herein comprise atleast one hydrophilic unit which is unsaturated carboxylic acid or itsderivative, and at least one hydrophobic unit which is a C8 to C30 alkylester or oxyethylenated C8-C30 alkyl ester of unsaturated carboxylicacid. The unsaturated carboxylic acid is preferably acrylic acid,methacrylic acid or itaconic acid. Examples can be made of material soldunder trade name Aculyn-22 by the company Rohm & Haas, materials soldunder trade names Pemulen TR-1, Pemulen TR-2, Carbopol 2020, CarbopolUltrez-21 by the company Noveon, and materials sold under the tradenames Structure 2001 and Structure 3001 by the company National Starch.Another preferable associative polymer for use in the polymer thickeningsystems of the present invention include polyether polyurethane, forexample materials sold under the trade name Aculyn-44 and Aculyn-46 bythe company Rohm and Haas. Another preferable associative polymer foruse herein is cellulose modified with groups comprising at least oneC8-C30 fatty chain, such as the product Natrosol Plus Grade 330 CS soldby the company Aqualon.

Non-associative cross-linked polycarboxylic polymers for use herein canbe chosen, for example, from:

(i) cross-linked acrylic acid homopolymers;

(ii) copolymers of acrylic or (meth)acrylic acid and of C1-C6 alkylacrylate or (meth)acrylate.

Preferable polymers are the products sold under the names Carbopol 980,981, 954, 2984, 5984 by the company Noveon or the products sold underthe names Synthalen M, Synthalen L and Synthalen K by the company 3VSigma, or the product sold under the name Aculyn-33 by the company Rohmand Haas.

The polysaccharides for use herein are, for example, chosen fromglucans, modified and unmodified starches (such as those derived, forexample, from cereals, for instance wheat, corn or rice, fromvegetables, for instance yellow pea, and tubers, for instance potato orcassaya), amylose, amylopectin, glycogen, dextrans, celluloses andderivatives thereof (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans,lignins, arabans, galactans, galacturonans, chitin, chitosans,glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acidsand pectins, alginic acid and alginates, arabinogalactans, carrageenans,agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums,karaya gums, carob gums, galactomannans, such as guar gums, and nonionicderivatives thereof (hydroxypropyl guar) and bio-polysaccharides, suchas xanthan gums, gellan gums, welan gums, scleroglucans, succinoglycansand mixtures thereof.

For example, suitable polysaccharides are described in “Encyclopedia ofChemical Technology”, Kirk-Othmer, Third Edition, 1982, volume 3, pp.896-900, and volume 15, pp. 439-458, in “Polymers in Nature” by E. A.MacGregor and C. T. Greenwood, published by John Wiley & Sons, Chapter6, pp. 240-328, 1980, and in “Industrial Gums—Polysaccharides and theirDerivatives”, edited by Roy L. Whistler, Second Edition, published byAcademic Press Inc., the content of these three publications beingentirely incorporated by reference.

The polysaccharide is preferably a bio-polysaccharide, particularlypreferable are bio-polysaccharides selected from xanthan gum, gellangum, welan gum, scleroglucan or succinoglycan, for example material soldunder the name Keltrol® T by the company Kelco and the material sold bythe name Rheozan® by the company Rhodia Chimie

Another preferable polysaccharide is hydroxypropyl starch derivative,particularly preferable hydroxypropyl starch phosphate, for example thematerial sold under the name Structure XL® by the company NationalStarch.

Suitable for use herein are salt tolerant thickeners, including but notlimited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methylcellulose, ethyl cellulose (available as AQUACOTE™), hydroxyethylcellulose (NATROSOL™), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (available as KLUCEL™), hydroxyethyl ethylcellulose, cetyl hydroxyethyl cellulose (available as NATROSOL™ Plus330), N-vinylpyrollidone (available as POVIDONE™), Acrylates/Ceteth-20Itaconate Copolymer (available as STRUCTURE™ 3001), hydroxypropyl starchphosphate (available as STRUCTURE™ ZEA), polyethoxylated urethanes orpolycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDI copolymer(available as ACULYN™ 44), PEG-150/Stearyl/SMDI copolymer (available asACULYN™ 46), trihydroxystearin (available as THIXCIN™), acrylatescopolymer (e.g. available as ACULYN™ 33) or hydrophobically modifiedacrylate copolymers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer(available as ACULYN™ 22), acrylates/steareth-20 methacrylatecrosspolymer (available as ACULYN™ 88), acrylates/vinyl neodecanoatecrosspolymer (available as ACULYN™ 38), acrylates/beheneth-25methacrylate copolymer (available as ACULYN™ 28), acrylates/C10-30 alkylacrylate crosspolymer (available as Carbopol® ETD 2020), non-ionicamphophilic polymers comprising at least one fatty chain and at leastone hydrophilic unit selected from polyether urethanes comprising atleast one fatty chain, and blends of Ceteth −10 phosphate, Di-cetylphosphate and Cetearyl alcohol (available as CRODAFOS™ CES).

Optional Surfactants

The compositions according to the present invention may comprise one ormore surfactants. Surfactants suitable for use herein generally have alipophilic chain length of from 8 to 30 carbon atoms and can be selectedfrom anionic, nonionic, amphoteric and cationic surfactants and mixturesthereof. In one embodiment, the total level of surfactant is from 1% to60%, or from 2% to 30%, or from 8% to 25%, or from 10% to 20% by weight.

The compositions of the invention preferably comprise a mixture ofanionic and amphoteric surfactants with one or more nonionicsurfactants. Anionic components may be present in the range from 0.1% to20%, preferably from 0.1% to 15%, and more preferably from 5% to 15% byweight of the composition; amphoteric or nonionic components mayindependently be present in the range from 0.1% to 15% by weight,preferably from 0.5% to 10%, more preferably from 1% to 8% by weight.

As examples of anionic surfactants, which can be used, alone or asmixtures, mention may be made, for example, of salts (such as alkalinesalts, for example, sodium salts, ammonium salts, amine salts, aminoalcohol salts and magnesium salts) of the following compounds: alkylsulfates, alkyl ether sulfates, alkylamido ether sulfates,alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulphonates,alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates, a-olefinsulfonates, paraffin sulfonates; alkyl sulfosuccinates, alkyl ethersulfosuccinates, alkylamide sulfosuccinates; alkyl sulfosuccinamates;alkyl sulfoacetates; alkyl ether phosphates; acyl sarcosinates; acylisethionates and N-acyltaurates. The alkyl or acyl radical of all ofthese various compounds, for example, comprises from 8 to 24 carbonatoms, and the aryl radical, for example, is chosen from phenyl andbenzyl groups. Among the anionic surfactants, which can also be used,mention may also be made of fatty acid salts such as the salts of oleic,ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenatedcoconut oil acid; acyl lactylates in which the acyl radical comprisesfrom 8 to 20 carbon atoms. Weakly anionic surfactants can also be used,such as alkyl-D-galactosiduronic acids and their salts, as well aspolyoxyalkylenated (C₆-C₂₄) alkyl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylaryl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylamido ether carboxylic acids and theirsalts, for example, those comprising from 2 to 50 ethylene oxide groups,and mixtures thereof. Anionic derivatives of polysaccharides, forexample carboxyalkyl ether of alkyl polyglucosides, can be also used.

The nonionic surfactants are compounds that are well known (see, forexample, in this respect “Handbook of Surfactants” by M. R. Porter,published by Blackie & Son (Glasgow and London), 1991, pp. 116-178).They can be chosen, for example, from polyethoxylated, polypropoxylatedand polyglycerolated fatty acids, alkyl phenols, α-diols and alcoholscomprising a fatty chain comprising, for example, from 8 to 18 carbonatoms, it being possible for the number of ethylene oxide or propyleneoxide groups to range, for example, from 2 to 200 and for the number ofglycerol groups to range, for example, from 2 to 30. Mention may also bemade of copolymers of ethylene oxide and of propylene oxide, condensatesof ethylene oxide and of propylene oxide with fatty alcohols;polyethoxylated fatty amides preferably having from 2 to 30 mol ofethylene oxide and their monoethanolamine and diethanolaminederivatives, polyglycerolated fatty amides, for example, comprising onaverage from 1 to 5, and such as from 1.5 to 4, glycerol groups;polyethoxylated fatty amines such as those containing from 2 to 30 molof ethylene oxide; oxyethylenated fatty acid esters of sorbitan havingfrom 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fattyacid esters of polyethylene glycol, alkylpolyglycosides,N-alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄)alkylamineoxides or N-acylaminopropylmorpholine oxides.

The amphoteric surfactants can be chosen, for example, from aliphaticsecondary and tertiary amine derivatives in which the aliphatic radicalis chosen from linear and branched chains comprising from 8 to 22 carbonatoms and comprising at least one water-soluble anionic group (forexample carboxylate, sulfonate, sulfate, phosphate or phosphonate);mention may also be made of (C₈-C₂₀)alkylbetaines, sulfobetaines,(C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines or(C₈-C₂₀)alkylamido(C₁-C₆)alkylsulfobetaines.

Among the amine derivatives, mention may be made of the products soldunder the name Miranol, as described, for example, in U.S. Pat. Nos.2,528,378 and 2,781,354 and having the structures of:R₂—CONHCH₂CH₂—N⁺(R₃)(R₄)(CH₂COO⁻), in which: R₂ is chosen from alkylradicals derived from an acid R₂—COOH present in hydrolysed coconut oil,and heptyl, nonyl and undecyl radicals, R₃ is a β-hydroxyethyl group andR₄ is a carboxymethyl group; and of R₅—CONHCH₂CH₂—N(B)(C), wherein Brepresents —CH₂CH₂OX′, C represents —(CH₂)_(z)—Y′, with z=1 or 2, X′ ischosen from the —CH₂CH₂—COOH group and a hydrogen atom, Y′ is chosenfrom —COOH and —CH₂—CHOH—SO₃H radicals, R₅ is chosen from alkyl radicalsof an acid R₅—COOH present in coconut oil or in hydrolysed linseed oil,alkyl radicals, such as C₇, C₉, C₁₁ and C₁₃ alkyl radicals, a C₁₇ alkylradical and its iso form, and unsaturated C₁₇ radical. These compoundsare classified in the CTFA dictionary, 5th edition, 1993, under thenames disodium cocoamphodiacetate, disodium lauroamphodiacetate,disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodiumcocoamphodipropionate, disodium lauroamphodipropionate, disodiumcaprylamphodipropionate, disodium capryloamphodipropionate,lauroamphodipropionic acid, and cocoamphodipropionic acid. Salts ofdiethyl aminopropyl cocoaspartamid can be also used.

The cationic surfactants may be chosen from: A) the quaternary ammoniumsalts of general formula (VII) below:

wherein X⁻ is an anion chosen from halides (chloride, bromide andiodide), (C₂-C₆)alkyl sulfates, such as methyl sulfate, phosphates,alkyl and alkylaryl sulfonates, and anions derived from organic acids,such as acetate and lactate, andi) the radicals R₁ to R₃, which may be identical or different, arechosen from linear and branched aliphatic radicals comprising from 1 to4 carbon atoms, and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals can comprise at least one hetero atom such as oxygen,nitrogen, sulfur and halogens. The aliphatic radicals are chosen, forexample, from alkyl, alkoxy and alkylamide radicals,R₄ is chosen from linear and branched alkyl radicals comprising from 16to 30 carbon atoms. The cationic surfactant is, for example, abehenyltrimethylammonium salt (for example chloride).ii) the radicals R₁ and R₂, which may be identical or different, arechosen from linear and branched aliphatic radicals comprising from 1 to4 carbon atoms, and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals can comprise at least one hetero atom such as oxygen,nitrogen, sulfur and halogens. The aliphatic radicals are chosen, forexample, from alkyl, alkoxy, alkylamide and hydroxyalkyl radicalscomprising from 1 to 4 carbon atoms; R₃ and R₄, which may be identicalor different, are chosen from linear and branched alkyl radicalscomprising from 12 to 30 carbon atoms, the said alkyl radicals compriseat least one function chosen from ester and amide functions.R₃ and R₄ are chosen, for example, from (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyland (C₁₂-C₂₂) alkylacetate radicals. The cationic surfactant is, forexample, a dicetyldimethyl ammonium salt (for example chloride);

B)—the quaternary ammonium salts of imidazolinium, such as that offormula (VIII) below:

in which R₅ is chosen from alkenyl and alkyl radicals comprising from 8to 30 carbon atoms, for example fatty acid derivatives of tallow,

R₆ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals and alkenyl andalkyl radicals comprising from 8 to 30 carbon atoms, R₇ is chosen fromC₁-C₄ alkyl radicals, R₈ is chosen from a hydrogen atom and C₁-C₄ alkylradicals, and X⁻ is an anion chosen from halides, phosphates, acetates,lactates, alkyl sulfates, alkyl sulfonates and alkylaryl sulfonates.In one embodiment, R₅ and R₆ are, for example, a mixture of radicalschosen from alkenyl and alkyl radicals comprising from 12 to 21 carbonatoms, such as fatty acid derivatives of tallow, R₇ is methyl and R₈ ishydrogen. Such a product is, for example, Quaternium-27 (CTFA 1997) orQuaternium-83 (CTFA 1997), which are sold under the names “Rewoquat®”W75, W90, W75PG and W75HPG by the company Witco,C)—the diquaternary ammonium salts of formula (IX):

in which R₉ is chosen from aliphatic radicals comprising from 16 to 30carbon atoms, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄, which may be identical ordifferent, are chosen from hydrogen and alkyl radicals comprising from 1to 4 carbon atoms, andX⁻ is an anion chosen from halides, acetates, phosphates, nitrates andmethyl sulfates. Such diquaternary ammonium salts, for example, includepropanetallowediammonium dichloride; andD)—the quaternary ammonium salts comprising at least one ester function,of formula (X) below:

in which:R15 is chosen from C1-C6 alkyl radicals and C1-C6 hydroxyalkyl anddihydroxyalkyl radicals;R16 is chosen from: a radical R19C(O)—, linear and branched, saturatedand unsaturated C1-C22 hydrocarbon-based radicals R20, and a hydrogenatom, R18 is chosen from: a radical R21C(O)—, linear and branched,saturated and unsaturated C1-C6 hydrocarbon-based radicals R22, and ahydrogen atom, R17, R19 and R21, which may be identical or different,are chosen from linear and branched, saturated and unsaturated C7-C21hydrocarbon-based radicals; n, p and r, which may be identical ordifferent, are chosen from integers ranging from 2 to 6; y is chosenfrom integers ranging from 1 to 10; x and z, which may be identical ordifferent, are chosen from integers ranging from 0 to 10; X— is an anionchosen from simple and complex, organic and inorganic anions; with theproviso that the sum x+y+z is from 1 to 15, that when x is 0, then R16is R20 and that when z is 0, then R18 is R22.

In one embodiment, ammonium salts of formula (X) can be used in which:R15 is chosen from methyl and ethyl radicals, x and y are equal to 1; zis equal to 0 or 1; n, p and r are equal to 2; R16 is chosen from: aradical R19C(O)—, methyl, ethyl and C14-C22 hydrocarbon-based radicals,and a hydrogen atom; R17, R19 and R21, which may be identical ordifferent, are chosen from linear and branched, saturated andunsaturated C7-C21, hydrocarbon-based radicals; R18 is chosen from: aradical R21C(O)— and a hydrogen atom. Such compounds are sold, forexample, under the names Dehyquart by the company Cognis, Stepanquat bythe company Stepan, Noxamium by the company Ceca, and Rewoquat WE 18 bythe company Rewo-Witco.

Method of Use

The hair colorant compositions usually are sold in kits comprising, inindividually packaged components such as separate containers, a tintcomposition (also called “dye cream” for emulsions or “dye liquid” forsolutions) comprising the oxidative dye precursors and an optionalalkalizing agent in a suitable carrier, and; an oxidizing composition(also called “hydrogen peroxide cream” for emulsions or “hydrogenperoxide liquid” for solutions) comprising the oxidizing agent. Theconsumer mixes the tint composition and oxidizing composition togetherimmediately before use to form a hair coloring composition and appliesthe hair coloring composition onto the hair. An alternative embodimentwherein the tint composition is provided in a solid form and mixed witha liquid oxidizing composition prior to application to the hair may alsobe utilized.

The tint and oxidizing compositions may be, independently from oneanother, prepared as so called thin liquids or creams. Typically thintype liquids have a viscosity of less than 1000 cPs. Upon mixing thecomponent parts, the resultant hair coloring or bleaching compositionspreferably have a viscosity of from 1000 to 60000 cPs, more preferablyfrom 2000 to 30000 cPs and most preferably from 3000 to 25000 cPs.Viscosity is measured using Brookfield viscometers with cone and plateattachment. For viscosities in the range of 0-12000 cPs the BrookfieldDV-11 viscometer with S42 plate is used. 2 ml sample of the compositionis equilibrated at 26.7° C. for three minutes before the readings aretaken at 1 rpm. For viscosities in the range of 12,000-60,000 cPs theBrookfield DV-1 viscometer with S52 plate is used. 0.5 ml sample of thecomposition is equilibrated for 1 minute at 26.7° C. before the readingsare taken at 1 rpm.

Application of the hair colorant composition to the hair may beundertaken in several ways. Application of the hair colorant compositionmay take place on the whole head of hair of an end user. By “whole headof hair” it is meant that the hair all over the head from the root ofthe hair to the tip of the hair is included in the application process.By contrast, the application of the hair colorant composition may takeplace on the root portion of the hair. The application to the rootportion of the hair may still be over the entire head of the end user,but application of the hair colorant composition is applied only to thesection of hair closest to the head (root portion), which is between0.01 mm to 4 mm from the scalp of the head. Also, application may takeplace on a portion of hair. Application of a portion of hair is commonlyreferred to as highlighting or lowlighting. The portion of hair may bephysically separated from the whole head of hair in a hair bundle or maybe a smaller portion of hair than the whole head of hair. A hair bundlemay be physically separated from a whole head of hair by a deviceincluding a plastic cap through which hair bundles are formed when hairis pulled through orifices in the plastic cap, metal foils encompassinga hair bundle, strand separators applied to hair at the root portion, orsimilar devices.

When present, an optional conditioning agent can be provided in a thirdcontainer. In the latter case, all three compositions can be mixedimmediately before use and applied together, or the content of the thirdcontainer can be applied (after an optional rinse step) as apost-treatment immediately after the hair colorant composition.

According to one method for oxidatively coloring hair, the methodcomprises mixing a tint composition and an oxidizing compositiontogether to form a hair colorant composition, applying a hair colorantcomposition to the hair, waiting for a period of 5-45 minutes, such as20-30 minutes, and then removing the hair colorant composition from thehair.

The methods of coloring hair also may further comprise working the haircolorant composition into the hair by hand or by a tool for a fewminutes to ensure uniform application to all of the hair. The haircolorant composition remains on the hair while the end hair colordevelops for a time period of 5 to 45 minutes. The consumer then rinseshis/her hair thoroughly with tap water and allows it to dry and/orstyles the hair.

Kits comprising one container for the first composition (tintcomposition) and one container for the second composition (oxidizingcomposition) can be advantageously used for this method. Optionally, athird composition may comprise an alkaline agent, such asmonoethanolamine (MEA). The kit further comprises instructions formixing and application of the hair colorant composition. The kit mayfurther include an object such as a mixing bowl, an application device,a dispensing device, gloves, hair strand separators, and any combinationof these objects. The kit also may comprise an additional container fora composition comprising a conditioning agent.

In one embodiment, the hair colorant kit may comprise (i) anindividually packaged oxidizing composition comprising an oxidizingagent; and (ii) an individually packaged tint composition. Theindividually packaged tint composition may comprise: (a) a2,6-diaminopyridine coupler and (b) a 2-methoxymethyl-1,4-diaminobenzenedeveloper. The oxidizing agent may be selected from any of the oxidizingagents described above such as, for example, hydrogen peroxide,inorganic or organic alkali-metal peroxides, inorganic perhydrate salts,alkyl and aryl peroxides, and or peroxidases, oxidase, and uricases andtheir substrates, percarbonates, persulfates, peroxymonocarbonates.Optionally, the tint composition may comprise an alkalizing agent suchas ammonia and ammonium salts and alkanolamines and their salts.

The hair colorant compositions may be used in a variety of packaging anddispensing devices. These dispensing devices can come in the form ofseparate devices that may be used independently or in combination withone another. Typically, the hair colorant compositions are containedwithin separate single-compartment or multi-compartment containers suchthat the tint composition and oxidizing composition can be storedseparately from one another before use. The tint composition and theoxidizing composition are mixed together in a mixing bowl or in adispensing device (such as a squeeze bottle, a squeeze foamer, pumpfoamer, and the like) and then applied to the consumer's hair via a tool(brush, comb, or the like) or by hand after being dispensed from thedispensing device.

Another packaging device involves storing the oxidizing components andtint components, along with any additional ingredients which include butare not limited to surfactants, antioxidants, stabilizers, chelants,thickening agents, and/or polymers, in a bottle or sachet, provided thatthe ingredients are in powdered form and anhydrous, wherein the haircoloring composition becomes activated by the addition of the prescribedamount of water.

The most common packaging device involves storing the oxidizingcomposition in a container such as a bottle, tube, squeeze foamer, pumpfoamer or a sachet and separately storing the tint composition in anadditional package such as a bottle, tube or sachet.

EXAMPLES

Hair colorant compositions tested were formulated by mixing a tintcomposition according to the formulation below in TABLE 1 with anoxidizing component in a 1:1 ratio. The oxidizing component is acommercially available WELLOXON® developer at 6% (20 vol) peroxideconcentration. In all the tests, a hair tress (white, brown and mixedblack/grey) was used (1.5 g tresses). To each tress, 3 g of the tintcomposition and 3 g of the oxidizing composition were applied for 30minutes at 30° C. The tresses were rinsed for 2 minutes, including 30seconds shampoo.

TABLE 1 Example Tint Component Formulations Ingredient Amount (wt. %)Oleic diethanolamide 12.0 Oleic Acid 5.0 Propylene Glycol 3.5 Ethanol7.0 Dipropylene Glycol 0.5 Propylene Glycol Methyl ether 9.0 Sodiumsulfite 0.159 Ammonium Acetate 0.8 EDTA 0.05 Erythorbic acid 0.42,6-diaminopyridine 0.546 2-methoxymethyl-1,4- 0.761 diaminobenzeneFragrance 1.000 Ammonia (28%) 7.14 Reverse-osmosis water QS to 100%

A swatch of white hair may be used to ascertain a color value of thehair colorant composition. Perceived color benefit may be furthernoticeable from the characteristics of the two additional swatches.After the hair is rinsed and dried, the color of the tress is measuredusing a 3700d Minolta Spectrophotometer.

Data from the spectrophotometer provide coordinates for both L*a*b* andLCh color spaces. In both the L*a*b* and LCh color spaces, the L* valuerefers to lightness on a scale of zero to 100, with lower valuesindicating a darker color. In the L*a*b* color space, the coordinate a*designates a position between red and green, with higher numbersindicating a redder shade and lower numbers representing a greenershade. The coordinate b* designates a position between yellow and blue,with higher numbers indicating a yellower shade and lower numbersrepresenting a bluer shade. In the LCh color space, the value Crepresents chroma, with higher values indicating a deeper, brightercolor and lower values indicating a less deep, duller color. The value Cin the LCh space is related to a* and b* in the L*a*b* space by therelationship C=[(a*)²+(b*)²]^(1/2). The coordinate h in the LCh spacerepresents hue angle, in which colors are represented as degree valuesfrom 0° to 360°.

Differences between the hair colorant compositions containing2,6-diaminopyridine in combination with2-methoxymethyl-1,4-benzenediamine and comparative 2-substituted1-4-diamine hair colorant compositions are determined from the L*, a*,b*, and C and h values, such that a negative value for any of ΔL*, Δa*,Δb*, and ΔC represents a lower value in hair colorant compositionscontaining 2-methoxymethyl-1,4-diaminobenzene than in hair colorantcompositions containing another 2-substituted 1-4-benzenediaminematerial. Color data for the hair colorant compositions prepared asdescribed are summarized in TABLES 2-4.

TABLE 2 Comparative color data on white hair from hair colorantcompositions comprising 2,6-diaminopyridine and2-methoxymethyl-1,4-benzenediamine combination vs. a comparative2,6-diaminopyridine with another 2-substituted 1-4-benzenediaminematerial combination. 2,6-diaminopyridine +2-methoxymethyl-1,4-benzenediamine or p-toluenediamine Visual ExamplePrimary L* a* b* C* h Result Example 1 2-methoxymethyl- 23.98 −5.44−8.14 9.79 236.27 Blue (less 1,4-benzenediamine violet overtones)Comparative p-toluenediamine 21.73 −4.76 −9.28 10.43 242.85 DarkerExample 1 Blue Δ(2-methoxymethyl-1,4- 2.25 −0.68 1.14 −0.64 −6.58benzenediamine - PTD)

TABLE 3 Comparative color data on brown hair from hair colorantcompositions comprising 2,6-diaminopyridine and2-methoxymethyl-1,4-benzenediamine combination vs. a comparative2,6-diaminopyridine with another 2-substituted 1-4-benzenediaminematerial combination. 2,6-diaminopyridine +2-methoxymethyl-1,4-benzenediamine or p-toluenediamine Visual ExamplePrimary L* a* b* C* h Result Example 2 2-methoxymethyl- 23.83 −4.18−2.93 5.11 214.99 Darker 1,4-benzenediamine Blue (less violet overtones)Comparative p-toluenediamine 21.15 −3.47 −4.64 5.79 233.21 DarkerExample 2 Blue Δ(2-methoxymethyl-1,4- 2.68 −0.71 1.71 −0.68 −18.22benzenediamine - PTD)

TABLE 4 Comparative color data on 50% blended-gray hair from haircolorant compositions comprising 2,6-diaminopyridine and2-methoxymethyl-1,4-benzenediamine combination vs. a comparative2,6-diaminopyridine with another 2-substituted 1-4-benzenediaminematerial combination. 2,6-diaminopyridine +2-methoxymethyl-1,4-benzenediamine or p-toluenediamine Visual ExamplePrimary L* a* b* C* h Result Example 3 2-methoxymethyl- 22.23 −3.66−5.66 6.74 237.06 Darker 1,4-benzenediamine Blue (less violet overtones)Comparative p-toluenediamine 20.89 −3.42 −6.35 7.21 241.70 DarkerExample 3 Blue Δ(2-methoxymethyl-1,4- 1.34 −0.24 −0.69 −0.47 −4.64benzenediamine - PTD)

According to the color data in TABLE 2, on the white hair, eachoxidative hair colorant composition containing the 2,6-diaminopyridineand 2-methoxymethyl-1,4-benzenediamine combination exhibited a hue anglecorresponding to a blue tone with less violet overtones (more subtle) incomparison with the hue angle for the comparative example. The colordata in TABLE 3 for brown hair were consistent with the data from thewhite hair, in that the samples generally showed a color benefit arisingfrom a darker blue owing to the contributing hair pigmentation, butstill with less violet overtones. The color data in TABLE 4 from the 50%blended gray hair also showed a substantial color benefit in thecompositions containing the 2,6-diaminopyridine and2-methoxymethyl-1,4-benzenediamine combination. Though the color benefitvaried across the formulations on different hair colors, it will beunderstood that, in general, hair colorant formulations may be tailoredfor use on specific consumer hair colors. As such, a notable figure ofmerit with regard to color benefit is realization of the color benefiton at least one type of hair, not necessarily on all types of hair.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention belongs. The terminology used in thedescription herein is for describing particular embodiments only and isnot intended to be limiting. As used in the specification and appendedclaims, the singular forms “a,” “an,” and “the” are intended to includethe plural forms as well, unless the context clearly indicatesotherwise.

The term “independently selected from,” as used in the specification andappended claims, is intended to mean that the referenced groups can bethe same, different, or a mixture thereof, unless the context clearlyindicates otherwise. Thus, under this definition, the phrase “X¹, X²,and X³ are independently selected from noble gases” would include thescenario where X¹, X², and X³ are all the same, where X¹, X², and X³ areall different, and where X¹ and X² are the same but X³ is different.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

Though particular embodiments have been illustrated and described, itwould be obvious to those skilled in the art that various other changesand modifications can be made without departing from the spirit andscope of the invention. It is therefore intended to cover in theappended claims all such changes and modifications that are within thescope of this invention.

What is claimed is:
 1. A hair colorant composition comprising: (a)2,6-diaminopyridine coupler; (b) 2-methoxymethyl-1,4-diaminobenzenedeveloper; and (c) an oxidizing agent.
 2. The hair colorant compositionof claim 1, comprising by weight, based on the weight of the haircolorant composition: from 0.001% to 6% of said coupler; from 0.001% to6% of said developer; and from 0.1% to 10% of said oxidizing agent. 3.The hair colorant composition of claim 1, wherein said oxidizing agentis selected from the group consisting of hydrogen peroxide, inorganicand organic alkali-metal peroxides, inorganic perhydrate salts, alkyland aryl peroxides, peroxidases, oxidases, and uricases and theirsubstrates, percarbonates, persulfates, peroxymonocarbonates, andmixtures thereof.
 4. The hair colorant composition of claim 1, whereinsaid hair colorant composition comprises from 0.05% to 6% of saiddeveloper, based on the weight of the hair colorant composition.
 5. Thehair colorant composition of claim 1, further comprising an alkalizingagent.
 6. A method of treating hair, said method comprising: (i)combining a tint composition with an oxidizing composition to form ahair coloring composition, wherein said tint composition comprises2,6-diaminopyridine coupler and 2-methoxymethyl-1,4-diaminobenzenedeveloper, and wherein said oxidizing composition comprises an oxidizingagent; and (ii) contacting said hair with said hair coloringcomposition.
 7. The method of claim 6, further comprising separating ahair bundle from said hair, wherein said contacting of said haircomprises contacting said hair bundle with said hair coloringcomposition.
 8. The method of claim 6, wherein said hair is selectedfrom the group consisting of a whole head of hair, a root portion ofhair, and a hair bundle separated from a whole head of hair.
 9. A haircoloring kit comprising: (i) an individually packaged oxidizingcomposition comprising an oxidizing agent; (ii) an individually packagedtint composition comprising: (a) 2,6-diaminopyridine coupler; and (b)2-methoxymethyl-1,4-diaminobenzene developer.
 10. The hair coloring kitof claim 9, further comprising instructions for forming a hair coloringcomposition from the oxidizing composition and the tint composition. 11.The hair coloring kit of claim 9, further comprising instructions forcontacting hair with the hair coloring composition.
 12. The haircoloring kit of claim 9, further comprising an object selected from thegroup consisting of a mixing bowl, an application device, a dispensingdevice, gloves, hair-strand separators, and combinations thereof. 13.The hair coloring kit of claim 9, wherein said oxidizing agent isselected from the group consisting of hydrogen peroxide, inorganic ororganic alkali-metal peroxides, inorganic perhydrate salts, alkyl andaryl peroxides, peroxidases, oxidase, and uricases and their substrates,percarbonates, persulfates, peroxymonocarbonates, and mixtures thereof.14. The hair coloring kit of claim 9 wherein said tint compositionfurther comprises an alkalizing agent.